Synthesis and Application of Carbonated Fatty Acid Esters from Carbon Dioxide Including a Life Cycle Analysis

Abstract

Carbon dioxide can be used in various ways as a cheap C1 source. However, the utilization of CO2 requires energy or energy-rich reagents, which leads to further emissions, and therefore, diminishes the CO2-saving potential. Therefore, life cycle assessment (LCA) is required for each process that uses CO2 to provide valid data for CO2 savings. Carbon dioxide can be incorporated into epoxidized fatty acid esters to provide the corresponding carbonates. A robust catalytic process was developed based on simple halide salts in combination with a phase-transfer catalyst. The CO2-saving potential was determined by comparing the carbonates as a plasticizer with an established phthalate-based plasticizer. Although CO2 savings of up to 80 % were achieved, most of the savings arose from indirect effects and not from CO2 utilization. Furthermore, other categories have been analyzed in the LCA. The use of biobased material has a variety of impacts on categories such as eutrophication and marine toxicity. Therefore, the benefits of biobased materials have to be evaluated carefully for each case. Finally, interesting properties as plasticizers were obtained with the carbonates. The volatility and water extraction could be improved relative to the epoxidized system.

Chemically Modifying Vegetable Oils to Prepare Green Lubricants

“…Functionalization of the olefin functional groups of unsaturated fatty esters or free fatty acids of vegetable oils can be performed by various reactions such as epoxidization, carbonation, maleation, acrylation, hydroxylation, hydroformylation, reduction, thiol-ene addition, and polymerization to produce plasticizers, polyurethanes, adhesives, paints, coatings, and envirsonmentally friendly additives for lubricants [40,[67][68][69][70][71]. The different modes of chemical vegetable oil transformation to produce base stocks/additives for biolubricants are discussed below.…”

“…Schäffner et al [67] tested simple alkali halides combined with a phase transfer catalyst in the reaction of epoxidized methyl linoleate with CO2 to prepare the respective bis-carbonate. Sodium iodide and 15-crown-5 as well as the combination of potassium iodide and 18-crown-6 were proven to be very active catalyst systems in the model reaction at 100 °C, 100 bar, and 17 h with a conversion of 94% and 90%, respectively [139].…”

Convergent Activation Concept for CO2 Fixation in Carbonates

“…[15] More recently, Schäffner et al studied the utilization of potassium iodide in combination with various phase transfer catalysts for the synthesis of oleochemical carbonates. [16] From am echanistic point of view it is wellr ecognized that commonly employed catalysts,a lso alkali metal based systems,a ctivate only the epoxide during the reactionp rocess. [12b,13e,14b,f,17] Thec ombination of aL ewis acidic catalyst andL ewis basic co-catalyst might leadt od ual activation of the epoxide.…”

Poly(ethylene glycol)s as Ligands in Calcium‐Catalyzed Cyclic Carbonate Synthesis

“…[8] Recently,t he utilization of cyclic carbonates as sustainable monomers for non-isocyanate polyurethane (NIPU) synthesis [9] and buildingb locks in organic synthesis gained increasing interest. [19] However,c urrent reportsi ndicate that CO 2 can interact weakly with ether linkages of PEGs, which leads to enhanced CO 2 adsorption rates. [5] For the synthesis of terminal cyclic carbonates only al imited number of catalytic systemso perate at room temperature.…”

“…[5] For the synthesis of terminal cyclic carbonates only al imited number of catalytic systemso perate at room temperature. [19] However,c urrent reportsi ndicate that CO 2 can interact weakly with ether linkages of PEGs, which leads to enhanced CO 2 adsorption rates. In contrastt ot he synthesiso ft erminal cyclic carbonates from epoxides and CO 2 ,t here are al imited number of catalysts that are able to produce internal carbonates at temperatures below 100 8C.…”